Process for producing water-insoluble azo dyestuffs containing sulfonyl groups using a metal sulfinate

ABSTRACT

1. A PROCESS FOR PRODUCING A WATER-INSOLUBLE AZO DYESTUFF OF THE FORMULA   R1-(3-R2,5-(R3-O2S-)-1,4-PHENYLENE)-N=N-(2-R4,5-R5-1,4-   PHENYLENE)-N(-R6)-R7   WHEREIN R1 IS H, NO2, CN, BR,-SO2CH3OR-SO2CH2H5; R2 IS H, -CH3, CN OR CL; R3 IS -CH3; -C2H5, -C4H9 OR PHENYL; R4 IS H, -CH3, -OC2H5, -NHCOCH3 OR -NHCONHCH2CH=CH2; R5 IS H OR -OCH3; R6 IS -CH2H5, -CH2CH2CN, -CH3, -C4H9 OR   -CH2CH2OCOCH3   AND R7 IS -C2H5, -CH2CH2-PHENYLM -CH2CH2CN, -CH2CH2OH, -CH2CH2SO2CH3, -CH2CH2CN, OR -CH2CH2OCOH3, SIA DPROCESS COMPRISING HEATING AN AZO DYESTUFF OF THE FORMULA   R1-(3-R2,5-R8-1,4-PHENYLENE)-N=N-(2-R4,5-R5-1,4-PHENYLENE)   -N(-R6)-R7   WHEREIN R1-R7 INCLUSIVE ARE AS AFORESAID AND R8 IS CL, BR OR NO2 WITH A METAL ORGANO SULFINATE WHEREIN THE METAL MOIETY IS SODIUM, POTASSIUM, AMMONIUM, CALCIUM, COPPER OR ZINC AND SAID ORGANO MOIETY IS METHYL, ETHYL, PROPYL, BUTYL OR PHENYL IN AN INERT ORGANIC SOLVENT AT A TEMPERATURE OF BETWEEN 20 AND 200*C. IN THE PRESENCE OF A COPPER COMPOUND, SAID METAL ORGANO SULFINATE BEING PRESENT IN A MOLAR RATIO AT LEAST EQUIVALENT TO THE NUMBER OF CL, BR OR NO2 GROUPS TO BE EXCHANGED FOR A SULFONYL GROUP AND SAID COPPER COMPOUND BEING CUPRONS OR CUPRIC OXIDE CHLORIDE, BROMIDE, IODIDE, SULFATE, RHODANIDE, ACETATE, NITRATE, CARBONATE, SULFIDE, CYANIDE, CHROMITE OR HEXACYANOFERRATE.

United States Patent M PROCESS FOR PRODUCING WATER-INSOLUBLE AZO DYESTUFFS CONTAINING SULFONYL GROUPS USING A METAL SULFINATE Hanswilli von Brachel, Offenbach, Main, and Dieter Cornelius, Darmstadt-Arheilgen, Germany, assignors to Cassella Farbwerke Mainknr Aktiengesellschaft, Frankfurt am Main, Fechenheim, Germany No Drawing. Continuation of abandoned application Ser. No. 877,821, Nov. 18, 1969. This application May 10, 1972, Ser. No. 252,348

Claims priority, application Germany, Nov. 20, 1968, P 18 09 921.3 Int. Cl. C09b 43/00; D06p 3/24, 3/52 US. Cl. 260-205 3 Claims ABSTRACT OF THE DISCLOSURE Production of water-insoluble azo dyestuffs containing at least one sulfonyl group which comprises reacting a monoor disazo dyestufi free from water-solubilizing groups and containing halogen or nitro substituents on an aryl or hetero aryl nucleus with a metal sulfinate in a molar ratio at least equivalent to the number of halogen atoms or nitro groups to be exchanged for a sulfonyl group and in a reaction inert organic solvent and optionally in the presence of copper compounds, said dyestuffs being useful for dyeing and printing of textile materials and being distinguished by excellent light and hot air fixing properties.

CROSS-REFERENCE TO RELATED APPLICATION This application is a continuation of application Ser. No. 877,821 filed Nov. 18, 1969 and now abandoned.

Mono and disazo dyestuffs containing in the diazo component sulfonyl groups linked to an aryl or hetero-aryl ring are already known. Of special interest are in this connection those azo dyestuffs containing in their diazo component three identical or different negative residues, such as nitro, cyano or sulfonyl groups: it is, however, particularly difficul-t to diazotize such diazo components.

It has, now been found that Water-insoluble mono or disazo dyestuffs containing sulfonyl groups are obtained by reacting, in an organic solvent that is indifferent to the reactants and optionally in the presence of copper compounds, mono or disazo dyestuffs free from water solubilizing groups and bearing in the diazo component halogen atoms or nitro groups linked to an aryl or hetero-aryl ring with metal sulfinates, the latter being present in a molar ratio at least equivalent to the number of halogen atoms or nitro groups to be exchanged for a sulfonyl group.

Aryl and hetero-aryl rings within the meaning of the present invention and bearing the halogen atoms or nitro groups to be exchanged are particularly phenyl, diphenyl and naphthyl residues as Well as quasi aromatic heterocyclic compounds, such as thiazolyl, benzimidazolyl and pyridyl residues. The fact the exchange reaction between the halogen or the nitro substituents and the sulfinate succeeds in the case of reacting final azo dyestuffs is surprising because very often the exchange of the respective halogen atoms or nitro groups in the diazo components prior to the formation of the azo dyestuff is impossible to carry out or does by far not run so smoothly.

The reaction according to the present invention may be carried out either with metal sulfinates alone or may preferably be accelerated by the addition of copper compounds. Suited metal sulfinates are particularly sodium, potassium, ammonium, calcium, copper or zinc alkyl and aryl-sulfinates, whereby the alkali sulfinates being available as large-scale industrial products are preferred. Such Patented Oct. 29, 1974 metal sulfinates are for instance: sodium-methyl, -ethyl, -propyl, -butyl and -phenyl-sulfinate and their derivatives that are substituted, for instance, by hydroxyl, alkoxy, or cyano groups or by halogen atoms. As copper compounds to be concurrently used under the present invention particularly suited are the copper (I) and copper (II) compounds, for instance, the respective chlorides, bromides, iodides, oxides, sulfides, sulfates, acetates and nitrates.

It is advisable to choose a reaction temperature of between 20 C. and 200 C., preferably of between 50 C. and C. The duration of the reaction depends to a large extent upon the constitution of the employed azo dyestuff containing the halogen atoms or nitro groups and varies from a few minutes to several hours. In general, it is easier to exchange bromine atoms and nitro groups than chlorine atoms and furthermore it is easier to exchange halogen atoms and nitro groups that are 0- positioned to the azo group than those being in or p-positioned. If the initial dyestuff contains more than one exchangeable halogen atom or nitro groups, in particular two chlorine or bromine atoms or nitro groups being in an o-position to the azo group, the corresponding dyestuffs containing more than one sulfonyl group are obtained.

The course of the reaction may easily be followed by means of chromatography so that the terminal point of the reaction may be determined without difficulty when in the chromatogram the spot of the initial dyestuff has disappeared.

Suitable solvents for the claimed process are, for instance, hydrocarbons, in particular aromatic hydrocarbons and their derivatives, such as benzene, toluene, xylene, chlorobenzenes and apart from them alcohols, esters, ethers, pyridine bases, quinoline, N,N-dimethylaniline, nitriles, such as acetonitrile, ketones, such as methyl-ethyl-ketone and cyclo-hexanone.

Dipolar aprotic solvents, such as acid amides, especially N,N-disnbstituted acid amides, N-alkyl-pyrrolidones, organic sulfoxides and sulfones have proved particularly suitable. The particularly advantageous effect of these solvents is due to the fact that they dissolve at least in part the sulfinates or the copper salts, thus accelerating the reaction. A particularly smooth course of the exchange reaction takes place, for instance, in the case of dimethyl-formamide, dimethylacetamide, hexamethylphosphoric acid triamide, N-methyl-pyrrolidone and dimethylsulfoxide. The dipolar aprotic solvents may also be diluted with other inert solvents, such as acetone, dioxan, chloro-benzene or nitro-benzene, whereby the course of the reaction is not adversely affected. It is advisable to choose the solvent itself and the amount of the solvent to be employed so that after the reaction the dyestuff containing sulfonyl groups precipitates, whereas the accompanying substances preferably remain dissolved.

The initial azo dyestuffs to be used under the present invention are, for instance, those water-insoluble disazo dyestuffs containing halogen atoms or nitro groups the diazo component of which derives from one of the following aromatic amines: haloanilines, such as oand m-bromo-anilines; halotuidines, such as 6-chloro-2- aminotoluene; halonitranilines, such as 2-chloro-, 2- bromoand 2-iodo-4-nitraniline, 4-chloro-2-nitraniline; halocyano-anilines, such as 2-bromo-4-cyanoaniline; halosulfonyl-anilines, such as 2-bromo-4-methylsulfonylaniline or 2-bromo-4-phenyl-sulfonyl-aniline; dinitranilines, such as 2,4-dinitraniline; nitro-cyanoanilines, such as 2-nitro-4-cyano-aniline; nitro-sulfonylanilines, such as 2 nitr0-4-ethylsulfonyl-aniline; dihaloanilines, such as 2,3-, 2,4-, 2,5- or 3,4-dibromo-aniline, 2,4-dichloro-5-methylaniline; trihalo-anilines, such as 3,4,6-trichloro-aniline; halocyano-nitranilines, such as 2-bromo-4-nitro-6-cyanoaniline; halocyano-alkylsulfonylanilines, such as 2- bromo-4-methylsulfonyl-6-cyanoaniline; halodinitro anilines, such as 2-cyano 4,6 dinitraniline; nitro-dicyanoanilines, such as 2,4-dicyano-6-nitritraniline; cyano alkylsulfonyl-nitranilines, such as 2-cyano-4-methylsulfonyl-6-nitraniline; halo-amino-naphthalines, such as 2-bromol-naphthyl-amine; and haloamino-azo compounds, such as 2-bromo-4-nitrophenylazo-(4'-amino-benzene) If the diazo component of the initial dyestulfs derives from a heterocyclic amine, the following compounds may be employed:

2 amino-S-bromo-thiazole, 2-amino-5-bromo-imidazole or 3,5-dibromo-4-aminopyridine.

The initial dyestulfs containing in the diazo component halogen atoms or nitro groups to be exchanged, may be prepared with the usual coupling components. Preferred coupling components are tertiary anilines, such as N,N-dialkyl anilines the alkyl groups of which may be unsaturated and/or substituted by negative residues, such as Cl, OH, O-alkyl, O-aryl, CO-O-alkyl, CN, N or alkylsulfonyl, and the nucleus of which may contain further substituents, such as alkyl, alkoxy, halogen or acylamino; further preferred coupling components are phenols, such as phenol, 0-, mand p-kresol or pyrazolones such as 1-phenyl-3-methyl-pyrazolone-5.

The dyestuffs to be prepared in accordance with the present invention are suited for the dyeing and printing of textile materials on the basis of cellulose esters, such as 2 /2-acetate and triacetate, polyamides, polyacrylicnitrile and especially of polyesters on the basis of polyethylene glycol terephthalate. They impart on those materials dyeings or prints that distinguish themselves by excellent fastness properties. The dyestulfs of the present invention are superior over the corresponding initial dyestuffs containing halogen or nitro groups with regard to their fastness to light and to hot-air fixing.

The following Examples are given for the purpose of illustrating the present invention.

Example 1 14.5 g. copper (I) bromide, 12 g. sodiummethyl-sulfinate and 40 g. 2-bromo 4 nitro-1-[4'-N-ethyl-N- cyano-ethyl-amino-phenyl-azo]-benzene are successively introduced into 100 cc. dimethyl-formamide and heated to 100 C. After 1 hours time the reaction mixture is allowed to cool down, then it is strongly sucked 01f and the residue is washed with little dimethyl-formamide and a great amount of water. Thus obtained are 31 g. 2-methylsulfonyl-4-nitro-1-[4 N ethyl-N-cyano-ethylaminophenyl-azo]-benzene which in a finely dispersed form dyes polyester fibers red shades.

According to thin layer chromatogram, infrared spectrum and mixed melting point the obtained dyestuif is identical with the product obtained by azo coupling from 2-methylsulfony1-4-nitraniline and N-ethyl-N-cyano-ethylaniline.

Example 2 36.8 g. 2,4-dinitro-1-[4'-N-ethyl-N-cyano-ethylaminophe'nylazo]-benzene, 4 g. copper (I) oxide and 15 g. potassium ethylsulfinate are successively introduced into 144 cc. dimethylsulfoxide and heated to 100 C. After 45 minutes time, the reaction mixture is allowed to cool down, then 50 cc. methanol are added. The reaction mixture is stirred for /2 hour, the precipitate being formed is strongly sucked oif, washed with little dimethyl-sulfoxide and much water. Thus obtained are 32 g. of a dyestuff that is identical with that obtained according to Example 1.

Example 3 48 g. 2-chloro-4,6-dinitro-l-(N-cyano-ethyl-N-phenethyl-amino-phenyl-azo)-benzene, 4 g. copper(I)oxide and 12 g. sodium ethyl-sulfinate are introduced into 500 cc. dimethylsulfoxide. The reaction mixture is stirred for 30 minutes at room temperature and subsequently added with stirring to 2,5 1. sodium chloride solution. The precipitate being formed is sucked 01f, stirred for several hours together with a 10% sodium cyanide solution, sucked off again and washed with much water. Thus obtained are 49 g. 2-chloro-4-nitro-6-ethylsulfonyl-1-[N- cyano-ethyl N phenyl-ethylamino-phenyl-azo]-benzene which, in a finely dispersed form, dyes polyester fibers reddish brown shades.

Example 4 46 g. 2-bromo-4-nitr0-6-cyano-1-[4'-diethylamino-2- acetylamino-phenyl-azo]-benzene, 0.8 g. copper(I)oxide and 15 g. potassium methyl-sulfinate are successively introduced into a mixture consisting of 100 cc. dimethyl sulfoxide and 100 cc. chloro-benzene and heated to 70 C. After 15 minutes time, the reaction mixture is allowed to cool down, strongly sucked off, washed with little dimethyl-sulfoxide, methanol and then with much water. Thus obtained are 41 g. 2-methylsulfonyl-4-nitro- 6-cyano-1- [4 diethyl-amino-2'-acetyl-amino-phenylazo]-benzene which, in a finely dispersed form, dye polyester fibers clear blue shades. According to thin layer chromatogram, infrared spectrum and mixed melting point the obtained dyestulf is identical with the product described in Example of US. Patent Application Ser. No. 791,775.

Example 5 48 g. 2-bromo-4,6-dinitro-1-[4-diethyl-amino-2'-acetylamino-phenyl-azo]-benzene and 9 g. copper(I)oyandide are introduced into 200 cc. dimethyl-sulfoxide and heated to C. After 15 minutes time, the exchange reaction between the bromine atom and the cyanide is terminated. 15 g. potassium methyl-sulfinate are added and the temperature is maintained for 1 0 minutes at 70-80 C. Subsequently, the reaction mixture is allowed to cool down, admixed with cc. methanol and strongly sucked 01f, washed with methanol and water. The obtained dyestulf is identical with the product obtained according to Example 4.

Example 6 42.5 g. 2-cyano-4,6-dinitro-1-[4'-diethylamino-2'-aceylamino-phenyl-azo]-benzene,"9 g. copper(I) cyanide and 12 g. sodium ethyl-sulfinate are introduced into cc. dimethylsulfoxide and heated to 50 C. After 15 minutes time the reaction mixture is allowed to cool down, admixed with 75 cc. methanol and sucked off and washed with methanol and water. The thus obtained dyestuif is identical with the products obtained according to Examples 4 and 5.

Example 7 40 g. 2,4 dinitro-1-[4' diethylamino-2'-acetylaminophenyl-azo]-benzene, 20 g. copper(I) iodide and 20 g. potassium phenyl-sulfinate are introduced into 150 cc. N- methylpyrrolidone and heated 80 C. After 30 minutes time, the reaction mixture is allowed to cool down and a solution consisting of 8 g. sodium cyanide dissolved in 40 cc. water is added dropwise. The precipitate is sucked olf and thoroughly washed with water. Thus obtained are 46 g. 2-phenylsulfonyl-4-nitro-1-[4 diethyl-amino-2- acetylamino-phenyl-azo]-'benzene which, in a finely dispersed form, dye polyester fibers reddish violet shades.

The following table enumerates further azo dyestulfs containing sulfonyl groups obtained according to the present invention. These dyestutfs are characterized by their shades when applied onto polyester fibers and obtained by reacting the initial dyestutf of the given formula with 1 or 2 moles of a metal sulfinate according to the methods described in the foregoing Examples.

General formula of the initial dyestuffs:

R R1 -N=N -N\ R1 R Bl Shade on polyester fabric of the Employed sulfinate final dyestufi gh rellg lifin ans egiiftaining 8 01' 5 011 R1 R1 R3 R4 R5 R6 R )6 Ca++- group: H H Br H H CHgCHzCaHs CH CH ON 1 mol 0 H so X Golden ellow. H H No, H H CHzCHgCN onionion imoloin sofx Yellow. H CH; 01 H H C2H5 CHZCHQOH 1 mol CH5SO;X Golden yellow. No, H Br H H 02H, CHgCH CN 1m0lCzH5S02X Red. NO; H N03 OH; H CH3 CHzCHzSOzCHa lmol 0113-801X Ruby. No, H NO; NHCOCH; H (Jim 2115 molCHg-SOgX Red violet CN H Br H H CHZCHQCN CHZCHQCOOCHQ 1m0lC2H5-SOzX Scarlet. ON H No: H H 04H, 2 g lmol CHa-SOzX Do. SO CH H Br 002115 H 0211' CHQCHQOCOCHQ lmol C2H5s0ix Red.

r H No, H H CHgCHgOCOCH: CHzOH OCOCH 2mols CHs-SOzX Orange SOzCzH; H BI H H. CzHs C2115 1 11101 CaH5SOzX ed. NO: ON Br H H cz o CHzCH OCOCH; 1 mol 0Hzsolx Violet. N0 CN N0, NHCONHCH CH=CH H CQHS C1H5 lmoloHr-sozx Blue. NO; ON NO; NHCOCH; OCH; cHioHtococHa H5 1m01C2H5'SO2X Do. ON ON Br NHCOCH; H 2 5 CH CH CN lmol 011 -80 X Violet. CN CN No, NHCOCH; H 02H; 01H; 1 mol CHrSOzX Blue violet. 0113501 CN B1 NHCOCH: H C2H5 02H: 1 11101 CzHr-SOzX DO. 1 CN NO] H H CHzCHzCN CHgCHgOCOCHg 2 111015 CHr-SOgX Ruby Example 8 15 g. zinc-methyl-sulfinate obtained by reduction of R2 5 methan sulfochloride with zinc, 45 g. 2-bromo-4-nitro-6- cyano-l-[4'-diethyl-amino 2 acetylamino-phenyl-azo1- Rr- -N=N N benzene and 0.2 g. copper(I)oxide are introduced into g I 150 cc. dimethylsulfoxide and heated for 2 hours to 80 2 R4 C. Subsequently, the reaction mixture is allowed to cool down, the precipitate being formed is strongly sucked 0E and washed with little dimethyl-sulfoxide, then with water. Thus obtained are, after drying, g. 2-methy1sulfony1-4-nitro-6-cyano-1-[4'-diethylamino 2' acetylamino-phenyl-azo1-benzene, which, in a finely dispersed form, dyes polyester fibers clear blue shades.

Example 9 Reaction conditions 1 hour }6 hour at 20 at 60 percent percent Copper compound employed:

OuJ 50 Without copper salt What we claim is: 1. A process for producing a water-insoluble azo dyestuif of the formula CH CH OCOCH and R is C H CH CH -phenyl, '-CH CH CN, --CH CH OH, CH CH SO CH --CH CH COOCH or --CH CH OCOH said process comprising heating an azo dyestuif of the formula wherein R1-R7 inclusive are as aforesaid and R is Cl, Br or N0 with a metal organo sulfinate wherein the metal moiety is sodium, potassium, ammonium, calcium, copper or zinc and said organo moiety is methyl, ethyl, propyl, butyl or phenyl in an inert organic solvent at a temperature of between 20 and 200 C. in the presence of a copper compound, said metal organo sulfinate being present in a molar ratio at least equivalent to the number of Cl, Br or N0 groups to be exchanged for a sulfonyl group and said copper compound being cuprous or cupric oxide, chloride, bromide, iodide, sulfate, rhodanide, acetate, nitrate, carbonate, sulfide, cyanide, chromite or hexacyanoferrate.

2. The process of claim 1 wherein said temperature is between 20 and C.

3. The process of claim 1 wherein said temperature is between 50 and 100 C. I

(References on following page) References Cited UNITED STATES PATENTS Landers 260607 A Felix et a1. 260-60 7 A X Dickey et a1. 260152 Gregory 260-607 A X Markgraf et a1. 260607 A Weaver et a1. 260-207.1

OTHER REFERENCES 8 Theilheimer: Synthetic Methods of Organic Chemistry, -vol. 2, pp. 188 and 189 (1949).

Theilheimer: Synthetic Methods of Organic Chemistry vol. 3, p 243 (1949).

Kauffman: J. Chem. Eng. Data, v01. 14, No. 4, pp. 498-499 (1969).

FLOYD D. HIGEL, Primary Examiner U.S. C1. X.R.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Hanswilli von Brachel and Dieter Cornelius Patent No.

Inventor(s) It is ce and that said Col. 2, line Col. 3, line Col. 4, line 'line sulfinate line Col. 5, line 65,

rtified that error appears in the above-identified patent Letters Patent are hereby corrected as shown below:

61, "halotuidines" should read halotoluidines 60, "ethylsulfinate" should read methylsulfinate-- 3l, "cyandide" should read cyanide 46, "ethyl-sulfinate" should read methyl- 60, "up to" should be inserted after "heated".

"CuCl'Y should read CuCl Signed and Sealed this T iventy-fourth D 3) Of October 1978 Q [SEAL] Attest:

RUTH C M S DONALD W. BANNER Amsting Commissioner of Patents and Trademarks 

1. A PROCESS FOR PRODUCING A WATER-INSOLUBLE AZO DYESTUFF OF THE FORMULA 